Process for purifying petroleum with multi-phase alkaline treating solutions of alkali metal salts of solutizers and process for regenerating said solutions



F. w. BROOKS, JR. ETAL 2,987,469

June 6, 1961 PROCESS FOR PURIFYING PETROLEUM WITH MULTL-PHASE ALKALINE TREATING SOLUTIONS OF ALKALI METAL SALTS OF SOLUTIZERS AND PROCESS FOR REGENERATING SAID SOLUTIONS l4 Sheets-Sheet 1 Original Filed Jan. 30, 1956 FI G.I

NORMALITY AND WEIGHT COMPOSITION OF SYSTEM,

POTASSIUM CRESYLATE,POTASSIUM HYDROXIDE,AND WATER AT 90F.

NOTEI SHADED AREA SHOWS RECOMMENDED COMPOSITIONS OF CONVENTIONAL POTASSIUM CRESYLATE TREATING SOLUTIONS POTASSIUM CRESYLATE IOO WT.

PHASE BOUNDARY INE AT 90 WATER IOOWT% A 4 e 7 a B I 2 3 5 POTASSIUM HYDROXIDE POTASSIUM HYDROXIDE -Z- NORMALITY INVENTORS.

Frank W.Brooks,Jr. CloiborneA. Duval,Jr.

AGENT.

F. w. BROOKS, JR. EI'AL 2,987,469

June 6, 1961 PROCESS FOR PURIFYING PETROLEUM WITH MULTI-PHASE ALKALINE TREATING SOLUTIONS OF ALKALI METAL SALTS OF SOLUTIZERS AND PROCESS FOR REGENERATING SAID SOLUTIONS 14 Sheets-Sheet 2 Original Filed Jan. 30, 1956 FIG.2

ALKYL PHENOL EQUILIBRIUM 90F NOTEISHADED AREA SHOWS RECOMMENDED COMPOSITIONS OF CONVENTIONAL POTASSIUM SOLUTIZER TREATING SOLUTIONS POTASSIUM CRESYLATE IOO WT.%

EQUILIBRIUM ALKYL PHENOL/P CONTENT IN OIL PHASE OUND HASE 8 INVENTOR$ Frank W. Brooks,Jr

Cloiborn .Duvol,Jn W

Agent June 6, 1961 F. w. 00K

PROCESS R PURIFYING s TREATI SOLUTIONS v AND PROCESS 0r1g1na] Filed Jan. 30, 1956 ETAL 2,987,469 TROLEUM H MULTI-PH ALKALINE ALKALI METAL SALTS OF UTIZERS REGENERATING SAID SOLUTIONS 14 She ets-Sheet 5 Fl G. 3

WATER 90F NOTE. SHAD AREA SHOWS REGO ENDED COMPOSITIONS OF CONVENTIONAL POTASSIUM SOLUTIZER TREATING SOLUTIONS POTASEDIgMWTCgRESYLATE 1 51 giiu R IiI om fifi gfam TS WEST TEX.ST.RUN l i I 6 %%EJ%*I AY AVAV wwmu AVAKAVAYAVAVAA AV 2 "AYMAYY AVA vvvvvv SOLUTION I M VISCOSITY W I I A AAAAA C$@|OOF.' 2: 7777777 "A'AYYQA' 1V A'AYA'AV F ROXIDE WT);

I/VVENTORS. Frank W. Brooks,Jr. C Ioiborne A.Duvc|l,Jr

AGENT.

June 6, 1961 F. w. BROOKS, JR., ETAL 2,987,469

PROCESS FOR PURIF'YING PETROLEUM WITH MULTI-PHASE ALKALINE TREATING SOLUTIONS OF ALKALI METAL SALTS 0F SOLUTIZERS AND PROCESS FOR REGENERATING SAID SOLUTIONS Original Filed Jan. 50, 1956 14 Sheets-Sheet 4 POTASSIUM CRESYLATE EQUILIBRIUM ALKYL PHENOL (GRESOL) CONTENT IN OIL PHASE PPM.

A B WATER D POTASSIUM HYDROXIDE WIZ,

lNVENTORS.

Frank W.Brooks,Jr. Claiborne A.Duvc||,Jr.

AGENT.

June 6, 1961 F. w. BROOKS, JR.. ET AL 7,

PROCESS FOR PURIFYING PETROLEUM WITH MULTI-PHASE ALKALINE TREATING SOLUTIONS OF ALKALI METAL SALTS OF SOLUTIZERS AND PROCESS FOR REGENERATING SAID SOLUTIONS orlglnal Flled Jan. 50, 1956 14 Sheets-Sheet 5 FIG.5

PHASE DIAGRAM FOR-SYSTEM POTASSIUM HYDROXlDE-ALKYL PHENOL-WATER TEMPERATURE 80F.

I006 ALKYL- PHENOL 0 I0 20 a; .D so so 70 so 90 I00 POTASSIUM HYDROXIDE %WEIGHT Claiborne A.DuvoI,Jr

ybuw) AG EN T.

June 6, 1961 F BROOKS, JR. ETAL 2 9874 PROCESS FOR PURIF'YING PETROLEUM WITH MULTI-PHASE A TREATING SOLUTIONS O LKALINE F ALKALI METAL SALTS OF SOLUTIZERS AND PROCESS FOR REGENERATING SAID SOLUTIONS Or1g1na1 Filed Jan. 30, 1956 14 Sheets-Sheet 6 FIGS PHASE DIAGRAMS FOR SYSTEMS POTASSIUM CRESYLATE, POTASSIUM ISOBUTYRATE, POTASSIUM HYDROXIDE AND WATER 90F.

POTASSIUM CRESYLATE AND POTASSIUM ISOBUTYRATE,W'I'."/

WT. RATIO OF POTASSIUM ISOBUTYRATE TO CRESYLATE IN TOTAL MIXTURE DARY LINE TOP LAYERS BOTTOM LAYER D E F POTASSIUM a?? HYDROXIDE WT.%

//VI/EN7'0/?$.

Frank W. Brooks,Jr. Claiborne .DuvoI,Jr.

AGENT.

June 6, 1961 F. w. BROOKS, JR, ETAL 2 987 PROCESS FOR PURIFYING PETROLEUM WITH MULTI-PHASE ALKZILINE' TREATING SOLUTIONS OF ALKALI METAL SALTS OF SOLUTIZERS AND PROCESS FOR REGENERATING SAID SOLUTIONS Original Filed Jan. 30, 1956 14 Sheets-Sheet 7 FIG.7

PHASE DIAGRAMS FOR SYSTEM POTASSIUM CRESYLATE, POTASSIUM METHYLMERCAPTIDEPOTASSIUM HYDROXIDE AND WATER 90E POTASSIUM CRESYLATE POTASSIUM METHYLMERCAPTIDE' WEIGHT% WT. RATIO OF POTASSIUM IPHAS PHASES METHYLMERCAPTIDE TO POTASSIUM CRESYLATE IN TOTAL MIXTURE TOP LAYER ASE BOUN A 8 WATER D E F POTASSIUM WI 7, HY DROXIDE IN VENTOHS.

Fronk W.Brooks,Jr. Claiborne A 'DuvuI,Jr.

uaw

AGENT.

June 6, 1961 F. w. BROOKS, JR.. ETAL 2,987,459

PROCESS FOR PURIFYING PETROLEUM WITH MULTI-PHASE ALKALINE TREATING SOLUTIONS OF ALKALI METAL SALTS 0F SOLUTIZERS AND PROCESS FOR REGENERATING SAID SOLUTIONS Or1g1na1 Filed Jan. 50, 1956 14 Sheets-Sheet 8 FIG.8

PHASE DIAGRAMS FOR SYSTEM POTASSIUM ORESYLATE, POTASSIUM BUTYLMERCAPTIDE,POTASSIUM HYDROXIDE AND WATER 90F.

POTASSIUM CRESYLATE AND POTASSIUM BUTYLMERCAPTIDE WT. RATIO OF POTASSIUM BUTYLMERCAPTIDE TO POTASSIUM CRESYLATE IN TOTAL MIXTURE TOP LAYE PHASE'BOUNDARY L B A WATER D E F POTASSIUM WT.% HYDROXIDE lNVE/VTORS.

Frank W. Brooks,Jr. Claiborne A.DuvoI,Jr.

June 6, 1961 F. w. BROOKS, JR. ETAL 2 987 4 PROCESS FOR PURIFYING PETROLEUM WITH MULTI-PI-IASE ALKALINE TREATIiIgDSgggIONS OF ALKALI METAL SALTS OF SOLUTIZERS ESS FOR REGENERATING SAID Or1g1na] Filed Jan. 30, 1956 SOLUTIONS l4 Sheets-Sheet 9 PHASE DIAGRAMS FOR SYSTEMS POTASSIUM CRESYLATE, POTASSIUM HEXYLMERCAPTIDE, POTASSIUM HYDROXIDE AND WATER 90F.

POTASSIUM ORESYLATE AND POTASSIUM HEXYLMEROAPTIDE WTRATIO OF POTASSIUM HEXYLMEROAPTIDE TO POTASSIUM CRESYLATE IN TOTAL MIXTURE TOP LAYER A R B WATER D POTASSIUM W1. 9:, HYDROXIDE wT. /o

INVENTORS. Frank. W. Brooks,Jr. Claiborne .DuvoI,J|

AGENT.

2,987,469 IFYING PETROLEUM WITH MULTI-PHASEI ALKALINE TIONS OF ALKALI METAL SALTS OF SOLUTIZERS C SOLUTIONS l4 Sheets-Sheet 10 June 6, 1961 F. w. BROOKS, JR. ETAL PROCESS FOR PUR TREATING sow AND PRO ESS FOR REGENERATING SAID Original Filed Jan. 30, 1956 FIG.|O

PHASE DIAGRAM FOR SYSTEM SODIUM HYDROXIDE-ALKYL PHENOL-WATER TEM PERATURE 80F 'IPHASE I Moi-MP vvv vvm oMMWw/Wv w IOC) SODIUM HYDROXIDE, %WE|GHT WATER (H2O) A O r in R 0 0 v .l U mm W3 mb 0 m AGENI.

J1me 1961 F. w. BROOKS, JR, EI'AL 2,937,459

I PROCESS FOR PURIFYING PETROLEUM WITH MULTI-PHASE ALKALINE TREATING SOLUTIONS OF ALKALI METAL SALTS OF SOLUTIZERS AND PROCESS FOR REGENERATING SAID SOLUTIONS Original Filed Jan. 30, 1956 14 Sheets-Sheet 12 RSH+H2O ETC.

TREATED PETROLEUM FIG.|2

REGENERATED KOR REGENERATED KOH z A 30 3s 2O '8 PETROLEUM 3s '3 FRACTIONS 7/ 2| 33 j 9 I2 i0 STEAM OR AIR .l3 Fl 6 RSH+H2O ETC. 53 57 RAW KOR FRACTION 62 so 4 p -KOH INVENTORS. Frcmk W.Brooks,Jr. STEAM OR AIR Clo|borne.uvol,Jr.

' June 6, 1961 F. w. BROOKS, JR. ETAL ,4 9

PROCESS FOR PURIFYING PETROLEUM WITH MULTI-PHASE ALKALINE TREATING SOLUTIONS OF ALKALI METAL SALTS OF SOLUTIZERS AND PROCESS FOR REGENERATING SAID SOLUTIONS Original Filed Jan. 30, 1956 14 Sheets-Sheet l3 KOR FIG.|4

94 85 88 95 RHS+H OH(.

8O KOH 84 8| J CRACKED ST.R. KERO.

IO 'I STEAM OR AIR I06 FIGJS F|G.l6 I23 I54 1 I52 EL, |2L8/ I Z I58 J I I24 I26 I32:- '56 I I INVENTORS Frank W. Brooks,Jr.

Claiborne Duvul,Jr.

June 6, 1961 F. w. BROOKS, JR. ETAL 2,987,469

PROCESS FOR PURIFYING PETROLEUM WITH MULTI-PHASE ALKALINE TREATING SOLUTIONS OF ALKALI METAL SALTS OF SOLUTIZERS AND PROCESS FOR REGENERATING SAID SOLUTIONS Original Filed Jan. 30, 1956 14 Sheets-Sheet l4 A TREATED SSOH+ TREATED ED. F|G.|7 gffififi fifigfij ABS .GASO. 0.00s WlZ/,R$H(s) I I 0.002 WT. RSH (5) PRESSURE DISTILLATE m? SSOH+ABS.GASO 0.02WT./,RSHs 208 S.R.GASO 207 7 f 2|4 i x 201 205; A KOR+KSR m A o 203 x KOR 206 227 EIB 2|9 234 KOR (236 235 #vvmrms Frank W.Brooks,Jr. Claiborne A.Duvul,Jr.

United States Patent O PROCESS FOR PURIFYING PETROLEUM WITH MULTI-PHASE ALKALINE TREATING SOLU- TIONS F ALKALI METAL SALTS OF SOLU- TIZERS AND PROCESS FOR REGENERATING SAID SOLUTIONS Frank W. Brooks, Jr., and Claiborne A. Duval, Jr., Beaumont, Tex., assignors to Socony Mobil Oil Company, Inc., a corporation of New York Original application Jan. 30, 1956, Ser. No. 562,241,

now Patent No. 2,850,434, dated Sept. 2, 1958. D1- vided and this application May 29, 1958, Ser. No.

13 Claims. (Cl. 208-234) The present invention relates to the removal of acidic organic material, especially mercaptans, from hydrocarbon fluids. More particularly, the present invention relates to the removal of mercaptans from hydrocarbon fluids directly or indirectly or directly and indirectly with a liquid mixture of water, solutizer salt of an alkali metal hydroxide and alkali metal hydroxide which liquid mixture is substantially immiscible with aqueous alkali metal hydroxide solutions.

It is recognized that aqueous alkaline solutions will extract acidic organic material from non-miscible organic liquids in a manner readily adapted to separation of the extracting medium and contained extracted acidic material from the treated non-miscible organic fluid. This concept was applied to the sweetening or removal of weakly acidic sulfur compounds from hydrocarbon fluids as soon ticularly alkyl and/or aryl mercaptans from hydrocarbon fluids, are the disclosures of D. L. Yabroif and his colleagues. Thus, in US. Patent No. 2,059,075 Yabrofi and Givins disclose that quaternary ammonium bases having a formula i [RrIIT-R4]OH in which R, to R are alkyl, unsaturated alkyl, aryl, or aralkyl radicals which may contain polar substitution groups selected from the class of -OH, -NH NO and halogen or heterocyclic radicals which are linked to the quarternary nitrogen atom by way of a carbon atom which carbon atom may or may not be part of the heterocyclic ring, can be used in conjunction with aqueous alkali metal hydroxide solutions 2.5 N to sodium hydroxide, i.e., 10 weight percent sodium hydroxide solution, to extract mercaptans from hydrocarbon fluids. These patentees disclose that the quaternary ammonium bases which they included within the class defined are soluble in 2.5 N (10 weight percent) NaOH, to the exent of about percent.

In US. Patent No. 2,066,925, Yabroff and Givins disclose that ternary sulfonium bases having the formula in which R R and R are alkyl, unsaturated alkyl, aryl or aralkyl radicals which may contain polar groups selected from the class of OH, NH NO and halogen, or heterocyclic radicals which are linked to the ternary sulfur atom by way of a carbon atom, which carbon atom may or may not be part of the heterocyclic ring. This class of solutizer is employed according to this disdisclosure in conjunction with alkali metal hydroxide in aqueous solutions in which the concentration of the sulfonium base does not exceed about 50 weight percent and the concentration of sulfonium base plus alkali metal hydroxide does not exceed 60 weight percent.

Another class of solutizers is disclosed in US. Patent No. 2,149,379. The class disclosed in this patent is the alkali metal salts of the lower fatty acids having 3 to 5.

carbon atoms in the molecule which are used in concentrat ions up to about 45 weight percent in aqueous alkali metal hydroxide solutions containing up to 20 weight percent alkali metal hydroxide. U.S. Patent No. 2,149,380 is directed specifically to the use of treating solutions containing alkali metal hydroxide up to about 40 weight percent which is about percent saturated with potassium isobutyrate.

In US. Patent No. 2,152,166 Yabrolf describes the use of aqueous alkaline treating solutions which are up to 2.5 i

N to alkali metal hydroxide, about 25 to about 75 percent polyhydroxy polar compounds such as propylene glycol, triethylene glycol, butylene glycol and about 5 to about 70 percent water.

Other solutizers such as the salts of the alpha hydroxy and alpha amino fatty acids having 3 to 7 carbon atoms in the molecule are disclosed in US. Patent No. 2,152,- 722; diamono alkanols having 3 to 5 carbon atoms (U.S. Patent No. 2,152,723); metal salts, particularly alkali metal salts of substituted fatty acids having up to 7 carbon atoms (U.S. Patent No. 2,156,577); alkali metal salts of phenyl acetic acid and hydroxy and amino phenyl acetic acid (U.S. Patent No. 2,164,851); amino diols such as amino dihydroxy propane (U.S. Patent No. 2,168,078); alkali metal alkyl phenolates (U.S. Patent No. 2,202,039); alkali metal alkyl phenolates in combination with an alkali metal salt of an aliphatic monocarboxylic acid having 1 to 8 carbon atoms (U.S. Patent No. 2,223,798); alkali metal salts of aliphatic dicarboxylic acids such as alkylene succinic acids which can be obtained by the reduction of phthalic acid and its homologues to the corresponding alicyclic dicarboxylic acid such as glutarate, adipate, undecene dicarboxylate and the like (U.S. Patent No. 2,229,- 995) are known to the art. However, all of these prior art treating or extracting solutions are single phase aqueous solutions in which neither the concentration of alkali metal hydroxide nor the concentration of solutizer salt is sufliciently high to cause the formation of a solutizer salt phase substantially immiscible with an aqueous alkali metal hydroxide phase. Thus, for example, the Henderson US. Patent No. 2,317,054 is directed to a method of extracting mercaptans in which the extracting medium is an equeous solution in which the concentration of the reaction product of the organic acidic materials and the alkali metal hydroxide does not exceed of saturation. Similarly, US. Patent No. 2,316,965 discloses a method of removing mercaptains from hydrocarbon fluids in which the concentration of the salt of the organic acidic material and alkali metal does not exceed the limit of solubility of the acid material employed.

In distinct contrast to the prior art extracting or treating solutions in which the concentration of solutizer salt does not exceed the solubility limit of that solutizer salt in the aqueous alkaline medium in which it is present, the extracting medium of the present invention is. a liquid containing free alkali metal hydroxide, an alkali metal salt or salts of one or more. solutizers and water which liquid is substantially immiscible in aqueous solutions of alkali metal hydroxide; For a better understanding of the present invention, reference will be made to the prior art use of alkali metal saltsof alkyl phenolates particularly potassium alkyl phenolates inconjunction with alkali metalhydroxide such as potassium hydroxide. I

For. many years, mixtures of hydrocarbons particularly petroleum distillates containing. organic sulfhydryls. such as alkyl mercaptans and aryl mercaptans or thiophenols. have been treated (l) to convert in situ. thesulfhydryls to inoffensively smelling polysulfides, or (2) to remove the sulfhydryls from the hydrocarbon mixture. Either procedure results, when the sulfhydryl content is reducedsufiiciently that the treated hydrocarbon mixture is negative in the doctor test in a hydrocarbon mixture which is said to be sweet. The methods by which such swee fractions are produced are generally known as sweetening.

Among the commercially practiced methods for removing organic sulfhydryls, i.e., alkyl and aryl mercaptans or mercaptans and thiophenols, all of the latter designations being widely used in the art, is that of contacting the hydrocarbon mixture containing mercaptans and/or thiophenols with aqueous alkaline solutions ranging incomposition from 5 normal potassium hydroxide-2'. normal. potassium alkyl phenolates to' 6 normal potassium hydroxide-3 normal potassium alkyl phenolate also-written 5, N KOH-2'N KAP to6 N KOH-3 N KAP. Itis also common usage to speak of the alkyl phenolates as. cresylates. The alkyl phenolates or cresylatesaregusually" those alkyl phenols extracted from the lower boiling fractions of petroleum such as gasoline andlight naphthas.

The alkyl phenolates or cresylates arev used in conjunction with potassium hydroxide because solutions containing free alkali metal hydroxide, such as potassium or sodium hydroxide, in combination with the alkali metal salts of the alkyl phenols or cresols have a greater power fororganic sulfhydryls than anaqueous solutionihaving the same concentration of alkali metal hydroxide but substantially devoid of alkali metal salts of'the alkyl phenols.

Aqueous solutions ranging in composition. from- 5 N'- KOH2 N KAP (21 weight percent. KOH, 24 weight percent-KAP (alkyl phenols) and 55 weight percent-water) to 6' N KOH-3 N KAP (24 weight percent KOH', 33 weight percent KAP and 43 weight percent water) are used because of their sulfhydryl extracting power. Hereinafter, the more commonly used terms, mercaptan; will be employed to include not onlythe alkylsulfhydryls but also the aryl sulfhydryls or thiophenols. The-limiting factors in the selection of solution strength areusually (-l:) the viscosity of the aqueous extracting solution, (2) the limit of solubility of the alkyl phenols in the aqueousalkali metal hydroxide solution, and (3 the alkyl phenol balance of the system, fraction being treated-extracting solution.

Such solutions are often difiicult to maintain at the desired strength in commercial operation. When the alkyl phenol content of the raw or untreated fraction is extremely low, the alkyl phenols of theextractingv solution. migrate to the oil fraction being treatedthereby lowering the alkyl phenol content of the extracting solution and reducing its extracting capability. On the other hand, when the alkyl phenol content of the raw or untreated. fractionis high, it is necessary to prewash the raw fraction to remove a portion of the alkyl phenols so that the alkyl phenol content of the extracting. solution will not be'unduly increased; The increase in the alkylphenoL content of the extracting solution reduces the concentta present invention.

4. tion of free or uncombined alkali metal hydroxide and dilution of the extracting solution by the water produced in the reaction of the alkyl phenols with the free alkali metal hydroxide.

As now used, the prior art method of removing mercaptans from mixtures of hydrocarbons involves contacting the'mixture of hydrocarbons with a single-phase aqueous. solution of" alkali; metal. hydroxide, or a single phase aqueous. solution of alkali metal hydroxide and alkali metal phenolates. The aqueous solution of alkali metal hydroxide only is not used to any great extent because of the low solubility of the 0 mercaptans in such solutions. Consequently, in general, the extracting solutions usually comprise free alkali metal hydroxide and solutizer salt. Because of the economies involved, the solutizer now used is the alkyl phenols and for various reasons the alkali metal hydroxide is potassium hydroxide.

Accordingly, present practice is to contact the mixture of'hydrocarbons containing mercaptans with an aqueous solution which is 5 to 6 normal to potassium hydroxide and 2 to 3 normal to potassium alkyl phenolates inone or more extraction stages. Usually the process is carried out in such a manner that the extracting solution is' con tinuously regenerated. Regeneration of the fouled or rich extracting'solution is accomplished either by steam distillation thereof whereby the mercaptides, i.e., the alkali metal salts of the mercaptans, are decomposed and the mercaptans volatilized or the mercaptides are converted topolysulfides by oxygen in the presence or absence of an oxidation promoter.

Either method of regeneration is costly for utilities, andin addition, when the-fouled extracting solution is regenerated withair, thealkyl phenolates are oxidized to acidic materials-which-form crystalline alkali metal salts which are precipitated, thus reducing the free alkalinity of: the regenerated. extracting solution. Consequently, a method of demercaptanizing or sweetening mixtures of hydrocarbons in which the volume of extracting solution to be regenerated can be reduced from that presently regenerated by steam or one in which the amount of solutionregenerated by oxidation is less than presently used has definite advantages over thepresent manipulations of such aqueous extracting solutions.

Before discussing in detail the principles of the present invention employing an extracting medium liquid at the extraction temperature comprising water, free alkali metal hydroxide and alkali metal salt of a solutizer which extracting medium is substantially immiscible with aqueous alkali metal hydroxide solutions, it is considered desirable to distinguish between the previously used treating or extracting solutionscontaining in solution in an aqueous alkali metal hydroxide solution an alkali metal salt of a solutizer and the extracting medium of the Since the solutizer solution most widely used in industrial operations is the potassium hydroxide-potassium alkylphenolate (.cresylate) solution, a comparison will be made between the aforementioned 6 N KOH3 N KAP solution and the potassium hydroxide-potassium cresylate-Water extracting medium of the present invention. This can be most readily accomplished by referenceto drawing, FIGURES 1,2, 3" andr4.

The-mercaptanextracting solutions now employed are three component systems in which the three components are (1) water, (2) alkali metal hydroxide, and (-3)- alkyl phenol. The system water, potassium hydroxide and potassium salts of the phenols present in petroleum fractions. boiling. between about 200 F. to about 650 F.,

hereinafter designated as potassium cresylate, hasbeen studied insufiicient detail to provide the data from which theternary. diagrams presented'as FIGURES l, 2; 3 and- 4 have been prepared.

FIGURE.- 1;is;-a ternary diagram of the system waterpotassium cresylate-potassium hydroxide. ApexpA'aof the: triangle represents 100 weight percent water, zero weight percent potassium hydroxide and potassium cresylate;

apex B represents 100 weight percent potassium hydrox ide, z ero weight percent water and potassium cresylate; and apex C represents 100 weight percent of the aforesaid salts of potassium designated potassium cresylate, zero weight percent water and potassium hydroxide. The sides of the triangle represent percentage composition by weight of various mixtures of two components. Thus, side AC represents mixtures of the components, water and potassium cresylate, between 100 weight percent water, zero weight percent potassium cresylate and 100 weight percent potassium cresylate, zero weight percent water. Side AB represents mixtures of the components water and potassium hydroxide between 100 weight percent water, zero weight percent potassium hydroxide and 100 weight percent potassium hydroxide, zero weight percent water. Side B-C represents mixtures of the components potassium hydroxide-potassium cresylate between 100 weight percent potassium hydroxide, zero weight percent potassium cresylate and 100 weight percent potassium cresylate, zero weight percent potassium hydroxide. Thus, any point within the triangle represents a mixture of the three components in certain concentrations expressed as weight percent.

It has been found that the system water-potassium hydroxide-potassium cresylate when in equilibrium at 90 F. forms a homogeneous one-phase system when the composition of the system is that represented by any point within the triangle to the left of line C-D, i.e., the phase boundary line and that the system is a heterogeneous, two-phase system when the composition thereof is represented by any point within the triangle to the right of the aforesaid line CDB, i.e., the phase boundary line.

The present invention is concerned with the use of mixtures of water-alkali metal hydroxide-alkali metal cresylate, i.e., alkali metal salts of the phenols extracted from petroleum fractions boiling within the range of about 200 F. to about 600 R, which are represented by points within the area bounded by the lines CD, DB and BC, i.e., the heterogeneous two-phase system, from which the extracting medium for direct, or indirect or both direct and indirect extraction of mercaptans are obtained.

It will be observed that superposed upon the left side of the basic ternary diagram are lines indicating the concentration expressed as Weight percent equivalent to potassium cresylate normalities of zero-to-S normal and equivalent to potassium hydroxide normalities of zeroto-9 normal. Thus, an aqueous 2 normal potassium cresylate solution contains about 2324 weight percent potassium cresylate. An aqueous normal potassium hydroxide solution contains about 21 weight percent potassium hydroxide. It follows then that the prior art aqueous potassium hydroxide-potassium cresylate solutions which are 2-3 normal potassium cresylate (KAP) and 5-6 normal potassium hydroxide are represented in FIGURES 1, 2, 3 and 4 by the cross-hatched area in each figure.

' In FIGURE 2 there is superposed upon the basic ternary diagram a family of curves indicating the compositions of various water-potassium cresylate-potassium hydroxide solutions which are in equilibrium with a hydro carbon oil phase having a constant alkyl phenol or cresol concentration expressed as parts of cresol per million parts of oil. Thus, the line bearing the legend 20, is drawn through the points on the diagram representing the various mixtures of water-potassium cresylate-potassium hydroxide which are in equilibrium with a hydrocarbon oil containing 20 parts of cresols per million parts of oil. Likewise, the line bearing the legend 30 is drawn through the points on the diagram representing the various mixtures of water-potassium cresylate-potassium hydroxide which are in equilibrium with a hydrocarbon oil containing 30 parts of cresols per million parts of oil.

Heretofore, it has been considered that the compositions of water-alkali metal hydroxide-alkali metal cresylate solutions were limited to those represented by the cross-hatched area of FIGURE 2, by reason of the migration of alkyl phenols or cresols from oil being treated to the treating solution dependent upon the composition of the treating solution. In other words, those skilled in the art taught that when the composition of the treating solution was other than that represented by he crosshatched area of FIGURE 2, the concentration of alkyl phenols or cresols in the oil being treated when in equilibrium with the treating solution having a composition represented by points outside the cross-hatched area would not be the same as the value from an oil in equilibbrium with a treating solution having a composition represented by a point within the cross-hatched area. As the family of curves in FIGURE 2 establish, the prior teaching was incorrect and the limitations imposed by the prior art as a result thereof has precluded the use of treating solutions of other compositions. In other words, prior to applicants discovery it was taught that compositions, such as represented by the sections KF and EC of the curve bearing the legend 30, were not in equilibrium with hydrocarbon oils containing 30 parts of cresols per million parts of oil and that consequently alkyl phenols would migrate from the oil to the treating solution or from the treating solution to the oil. As a consequence of migration from the oil to the treating solution, the capacity of the solution to extract mercaptans would be reduced by the equivalent of the alkali metal hydroxide neutralized by the cresols. In other words, the prior art taught that as the concentration of alkyl phenols (cresols) increased in the treating solution from the prior art maximum of about 2.2 normal (27 weight percent) such solution would not be in equilibrium with hydrocarbon oils containing 30 parts per million of cresols. In contrast, it has now been discovered that treating solutions having compositions represented by the points along the line bearing the legend 30, are in equilibrium with hydrocarbon oils containing 30 parts per million alkyl phenols. Thus, it has now been discovered that treating solutions of many compositions not contemplated by those skilled in the art are competent for treating hydrocarbon oils containing alkyl phenols as well as mercaptans. The importance of this discovery becomes apparent upon consideration of FIGURE 3.

Two families of curves are presented in FIGURE 3. Those drawn with continuous lines represent the mercaptan sulfur in oil in equilibrium with treating solutions of various compositions, while those drawn with discont-inuous lines represent the viscosity in centistokes of treating solutions of various compositions. Thus, the discontinuous line beginning at 2A represents the compositions of solutions having a constant viscosity of 2 centistokes. The discontinuous lines beginning at 5A and 12A represent'respectively the compositions of mixtures'having a constant viscosity of 5 to 12 centistokes. The mixtures represented by the points on the continuous line bearing the legend 0.044 are those which are in equilibrium with the oil shown containing 0.044 weight percent mercaptan sulfur, while the mixtures having compositions represented by points on the line bearing the legend 0.001 are those which are in equilibrium with the oil containing 0.001 Weight percent mercaptan sulfur. In other words, any mixture of water, potassium cresylates and potassium hydroxide having a composition represented by a point on the line bearing the legend 0.001 can be used to treat the gasoline to yield a treated gasoline containing 0.001 weight percent mercaptan sulfur. It will be noted that the presently used aqueous solutions of potassium hydroxid and potassium cresylate are only a small portion of the mixtures which can be used.

The significance of the data plotted in FIGURES 2 and 3 can be more readily recognized by reference to FIGURE 4 where the data from FIGURES 2 and 3 have been plotted together. The presently recommended aqueous prior art solutions which can be used to produce a treated gasoline having a mercaptan sulfur content of 0.001 weight percent are those having compositions represented by the triangular portion of the cross-hatched area in the upper right corner of the parallelogram. On the other hand, it is manifest that all mixtures of water, alkyl phenol and potassium hydroxide to the night of the dis- Continuous curve bearing the legend 0.001 are suitable for treating a petroleum fraction similar to the one shown having a mercaptan sulfur concentration greater than 0.001 to produce a treated petroleum fraction having a mercaptan sulfur concentration of about 0.001. The other discontinuous curves bearing respectively the legends 0.005, 0.010, 0.028 and 0.044 are interpreted in an analogous manner. These lines would be displaced for other oils or other mercaptan sulfur compounds.

While the use of solutions of water-alkali metal hydroxide-alkali metal alkyl phenolate having compositions falling on points outside the cross-hatched areas of FIG- URES 1, 2, 3 and 4 is not within the scope of the present invention, the present invention is concerned particularly with the use for extracting mercaptans from mixtures of hydrocarbons of solutions having compositions represented by points within the area of the ternary diagrams bounded by the lines BD, DC and CB, and particularly those having compositions represented by points on the line DC.

One advantage inherent in the use of the solutizer salt phase of solutions having compositions represented by points on line DC is the fact that the cost of the alkali metal hydroxide in the circulating treating solution is less than that of mixtures, the compositions of which are represented by points to the right of line DC. An advantage in the use of the solutizer salt phase of mixtures, the compositions of which are represented by points on the line DC or to the right thereof, is the ease of separation of the mercaptans from the treating solution and the small amount of the mixture required to treat a given volume of a mixture of hydrocarbons containing mercaptans.

Illustrative of the advantage of using the solutizer salt phase which is immiscible with aqueous alkali metal hydioxide solutions in the Kg value for such a solutizer salt phase.

Referring now to FIGURE 5 which is a ternary diagram of the system water-potassium hydroxide-alkyl phenol at 80 F. The ASTM distillation and API gravity of these alkyl phenols (cresols) is given in the following tabulation.

A solution having a composiiton represented by point A on FIGURE 5 comprising 19 Weight percent of the aforedescribed alkyl phenols, '44 weight percent potassium hydroxide and 37 weight percent water separates into a solutizer salt (cresylate) phase represented by the point on line R--S bearing the legend KOR and an aqueous potassium hydroxide solution represented by the point bearing the legend KOH. The aqueous potassium hydroxide solution contains 51 weight percent potassium hydroxide. The solutizer salt phase (substantially immiscible with the aforesaid 51 weight percent potassium hydroxide solution) is composed of 36.2 weight percent KOH, 36.6 weight percent alkyl phenols (cresols) and 27.2 weight percent water. a

The Kg values for the aforesaid cresylate phase and a 6 N KOH-3 N KAP solution were determined. These values are given in the following tabulation:

TO C-Thermofor catalytic cracked.

WTSR-West Texas straight run.

6 N KOH-3 N KAP: KORE-36 weight percent, KAP-26 weight percent, Hz038 weight percent.

Those skilled in the art will recognize that distribution coefiicients for the cresylate phase indicate a far greater extractive capacity than that of the prior art presently used 6 N KOH-3 N KAP solution. Thus, for example, the Kg values indicate that the cresylate phase (KOR solution) has about twice the capacity of the standard solutizer solution for n-amyl mercaptan. This indication is corroborated by the fact that at a given extraction medium to gasoline ratio the KOR phase reduces the mercaptan content of a hydrocarbon fluid to a lower value than is reached by using the standard solutizer solution and by the fact that at lower ratios the KOR phase reduces the mercaptan content of the hydrocarbon fluid to the same extent as the greater volume of standard solutizer solution. These facts are established by the data presented in the following tabulation:

[Hydrocarbon fluid: West Texas straight run gasoline. Mercaptan sulfur, percent wt. 0.129]

Standard Treating Medium Composition, wt. KOR Phase solutizer percent 6 N KOH- 3 N KAP Treating Ratio:

Vol. Treating Medium/ Vol. Gasoline 0.05 0. 10 0. 20 0.33 0. 20 Mercaptan sulfur, wt.

percent:

After 1st stage 0.0140 0.0065 0.0046 0.002 0.0123 After 2nd Stage 0.0024 0. 001 0.001 0.003

It will be noted that the KOR phase is as effective in removing mercaptans in two stages at a treating medium to gasoline ratio of 0.05 (1 volume of treating medium to 20 volumes of gasoline) as the standard 6 N KOH- 3 N KAP solution is at a treating ratio of 0.20 (4 volumes of treating medium to 20 volumes of gasoline). In other words, one volume of KOR phase will do the work of ,4 volumes of 6 N KOH-3 N KAP solutizer solution.

Similar results are obtained in extracting mercaptans from petroleum fractions boiling above the gasoline range as is manifest from even a cursory study of the following data.

These data establish that at a treating ratio of 0.20 the KOR phase removes in the first stage 73.5 percent of the mercaptan sulfur from the kerosine while at the same treating ratio the solutizer solution only removes 58.6 percent. In the second stage the removal of mercaptan sulfur is raised to 88.5 percent when using the KOR phase as the treating medium.

It was suggested by Yabroff and others particularly in US. Patent No. 2,202,039 that solutizer solutions having a viscosity greater than 37 /2 centistokes should not be used because of the uneconomical loss of entrained oil. On the other hand, it has been found that the loss of entrained oil actually is relatively and absolutely less with the KOR treating media of the present invention than with solutizer solution. The data supporting this assertion is presented in the following tabulation:

[Hydrocarbon fluid: West Texas sour gasoline. Feed: 10,000 barrels/day] That is to say, after dilution the KOR phase retains 1.6 barrels while the solutizer solution retains 9.2 barrels or approximately 6 times as much oil.

As was emphasized hereinbefore, mixtures of alkali metal hydroxide, alkyl phenol and water having composi. tions represented by points on the line DC, or to the right thereof, form two phases. As a consequence of this phenomenon, it is possible to treat mixtures of hydrocarbons by several methods taking advantage of this peculiarity of the system.

In the light of these facts and in accordance with the principles of the present invention the MOS phase of mixtures the compositions of which are represented by points to the right of the phase boundary line of the ternary diagrams for the system alkali metal hydroxide-solutizer or solutizer salt-water can be used to extract mercaptans from hydrocarbon fluids directly or indirectly or directly and indirectly. That is to say, the hydrocarbon fluid can be contacted with the MOS phase (a phase containing alkali metal hydroxide-alkali metal salt of a solutizer and water) to extract mercaptans in one or more stages, preferably two or more stages, to produce 2. treated hydrocarbon fluid of reduced mercaptan content and a fouled treating medium (fouled MOS phase), they treated hydrocarbon fluid separated irom the fouled treating medium otherwise denuded of mercaptans. This is direct extrac tion of mercaptans.

In indirect extraction of mercaptans, the hydrocarbon fluid is contacted with an aqueous alkali metal hydroxide solution with which the MOS phase is substantially im-' miscible to obtain a treated hydrocarbon fluid and a fouled treating medium (MOH). The fouled treating medium is then contacted with a lean, i.e., substantially mercaptan free or stripped MOS medium with which the fouled MOH treating medium is substantially immiscible.

The mercaptans extracted from the hydrocarbon fluid by the aqueous metal hydroxide solution migrate therefrom upon being mixed with the lean MOS medium whereby the lean MOS medium becomes fouled with the mercaptans directly extracted from the hydrocarbon fluid by the aqueous metal hydroxide solution and transferred from the fouled aqueous metal hydroxide solution to the lean MOS solution. In other words, the mercaptans are extracted from the hydrocarbon fluid directly by the alkali metal hydroxide solution and indirectly by the MOS phase. In other words, this is typical of the indirect extraction of mercaptans from hydrocarbon fluid by the MOS phase.

The mercaptan contained in hydrocarbon fluid can be extracted directly and indirectly simultaneously by the use of a heterogeneous two-phase extracting medium. That is to say, a mixture of alkali metal hydroxide, alkali metal salt of a solutizer and Water which has a composition represented by a point to the right of the phase boundary line of a ternary diagram for the system which forms two immiscible phases, i.e., a MOS phase and a MOH phase can be used as a two-phase treating agent. That is to say, a hydrocarbon fluid containing mercaptans is contacted with a two-phase treating agent. The alkali metal hydroxide phase extracts primarily the C-4 and lighter mercaptans While the MOS phase extracts the C-5 and higher mercaptans directly. However, through contact of the MOS with the MOH phase the mercaptans extracted by the MOH phase substantially immediately migrate to the MOS phase. Thus, there is extraction of the C-5 and higher mercaptans directly by the MOS phase and extraction of the C-4 and lighter mercaptans indirectly by the MOS phase.

Another example of the direct and indirect extraction of mercaptans with the MOS phase is that operation in which one hydrocarbon fluid is contacted with a lean MOH phase, another hydrocarbon fluid is contacted with a lean MOS phase, the treated hydrocarbon fluids are separated from the respective MOS and MOH phases, and the fouled MOH phase mixed with the fouled MOS phase. Here again the mercaptans in the fouled MOH phase migrate to the fouled MOS phase and we have extraction of mercaptans directly and indirectly with'the MOS phase. Thus, for example, referring to FIGURE 3 a solution having a composition represented by a point on line KL will separate into two phases. The MOS phase, i.e., the potassium hydroxide-potassium cresylate-water phase will have a composition represented by point K on the ternary diagram. The aqueous potassium hydroxide phase (MOH phase) will have a composition represented by the point L on the ternary diagram. The potassium hydroxide-potassium cresylate-water phase will contain about 64 percent potassium cresylate, about 23 percent water and about 13 percent potassium hydroxide and will be in equilibrium with a KOH phase containing about 54 percent KOH and 46 percent water. A hydrocarbon fluid, for example, a straight run gasoline, is contacted with the aforesaid MOR phase to obtain a treated gasoline and a fouled MOR phase. The treated gasoline is separated from the fouled MOR phase. The fouled MOR phase is then diluted with at least an equal amount of water and the solution steamed to hydrolyze the mercaptides to mercaptans and volatilize the mercaptans. This produces a dilute lean KOR phase which is then concentrated and is ready for use to extract more mercaptans. This is illustrative of the direct extraction of mercaptans with a MOS phase. Illustrative of the indirect extraction of mercaptans with a MOS phase is the use of the aforesaid KOH phase as an extracting medium. Thus, for example, a cracked gasoline is contacted with a KOH solution containing about 54 percent potassium hydroxide to produce treated gasoline and fouled KOH solution. The treated gasoline is separated from the fouled KOH solution and the fouled KOH solution intimately mixed with lean KOR solution, i.e., the aforesaid KOR solution containing 64 weight percent potassium cresylate, 13 weight percent potassium hydroxide and 23 percent Water. The mercaptans present in the fouled KOH solution migrate to the lean KOR solution. The KOR solution and the KOH solution being substantially immiscible the fouled KOR solution is separated from the regenerated or lean KOH phase. The separated lean KOH phase is then used to extract more mercaptans from the cracked gasoline. The KOR phase is diluted with at least an equal volume of water and steam stripped to remove the mercaptans. Upon concentration of the lean KOR phase the lean KOR phase is ready again to remove mercaptans from a fouled KOH phase. This is illustrative of the indirect extraction of mercaptans with a MOS phase.

Illustrative of the substantially simultaneous direct and indirect extraction of mercaptans by a MOS phase is the extraction of mercaptans from a straight run gasoline employing a two-phase heterogeneous treating medium such as one having a composition represented by point A on the ternary diagram FIGURE 5. Such a two-phase treating medium contains about 19 percent potassium cresylate, about 44 percent potassium hydroxide and about 37 percent water. The straight run gasoline is contacted with the two-phase treating agent whereby the KOH phase directly extracts the light mercaptans and the KOR phase directly extracts the heavy mercaptans. Since the KOR phase and the KOH phase are in intimate contact the mercaptans extracted by the KOH phase practically immediately migrate to the KOR phase. The treated gasoline is separated from the two-phase treating medium and the two-phase treating medium is permitted to separate into a fouled KOR phase and a lean KOH phase. The fouled KOR phase is separated from the lean KOH phase, stripped of the mercaptans in the conventional manner, and mixed with the lean KOH phase to provide a lean two-phase treating medium comprising the lean KOR phase and the lean KOH phase. In further illustration of indirect extraction of mercaptans with a MOS phase is the extraction of mercaptans from cracked gasoline with a lean KOH phase and extraction of mercaptans from a straight run gasoline with a lean KOR phase. Thus, for example, a mixture having a composition represented by point A on the ternary diagram FIGURE 5 is separated into a lean KOR phase having a composition reprsented by the point on the solubility line bearing the legend KOR and a KOH phase having a composition represented by a point on the ternary diagram FIGURE 5 bearing the legend KOH. The cracked gasoline is contacted with the lean KOH phase to obtain a treated cracked gasoline and a fouled KOH phase. The fouled KOH phase is separated from the treated cracked gasoline. A straight run gasoline is contacted with the lean KOR phase to obtain a treated straight run gasoline and a fouled KOR phase. The treated straight run gasoline is separated from the fouled KOR phase. The fouled KOH phase and the fouled KOR phase are then mixed with the result that the mercaptaus in the KOH phase migrate to the KOR phase. The fouled KOR phase is regenerated by steam stripping and the lean KOR phase is then ready for use in the treatment of further amounts of straight run gasoline. The lean KOH phase resulting from the intimate mixing of the fouled KOH phase with the fouled KOR phase upon separation from the fouled KOR phase is ready for 12 use in the extraction of mercaptans from cracked gasoline. Thus, this is illustrative of the direct extraction of mercaptans by the lean KOR phase and the indirect extraction of mercaptans by the lean KOR phase.

Those skilled in the art will appreciate that the phase boundary line or the solubility limit line in the ternary diagrams for the system potassium hydroxide-potassium cresylate-water shifts somewhat with temperature. Consequently, compositions given hereinbefore for the twophase mixture and for the KOR and KOH phases will change with a change in temperature to some extent. It also will be recognized by those skilled in the art that there are differences in the position of the phase boundary line or solubility line arising entirely from the basis for the preparation of the graph. That is to say, if the ternary diagram expresses the composition in terms of the conceneration of solutizer rather than in terms of the concentration of solutizer salt cursory examination will lead to a conclusion that there is a discrepancy which does not actually exist.

The foregoing detailed discussion of the system potassium hydroxide-potassium cresylate-water and the use of that system in the removal of mercaptans is merely illustrative of one segment of the present invention. Other ternary systems in which the alkyl phenols (cresols) are replaced by other solutizers and consequently alkyl phenolates (cresylates) are replaced by other solutizer salts exhibit the same phenomena. However, ternary systems of other solutizers exhibit a phenomenon not exhibited by the alkali metal hydroxide-alkali metal alkyl phenolate-water system. That is to say, that while both phases of the cresylate system remain liquid at usual treating temperatures of to F., the alkali metal salt phase of other systems tends to solidify instead of remaining liquid at usual extracting temperatures of 80 to 100 F. Consequently, for practical purposes the ternary system is converted to a quaternary system in which the salt phase is liquid at extraction temperatures by the introduction into the ternary system of a liquefier or co-solvent such as lower alcohols, i.e., aliphatic alcohols having not more than 5 carbon atoms in the molecule in amounts sufiicient to maintain the alkali metal salt phase liquid at temperatures of 80 to about F., water-soluble ketones such as acetone and the like and cresylates such as the alkali metal salts of the phenolic and/or acidic organic material present in petroleum oil fractions for example, straight run or cracked naphthas, gas oils, fuel oils can also be used as liquefiers or cosolvents.

Typical of the application of this invention to one of the traditional solutizers is the ternary system, potassium isobutyrate-potassium hydroxide-Water. The ternary diagram, FIGURE 6, shows the areas of single-phase and two-phase systems formed by diiferent concentrations of the three components of the system.

In a three component system of water-potassium hydroxide-potassium isobutyrate, i.e., an alkali metal salt of a lower fatty acid, those mixtures represented by the area to the left of the line bearing the legend Phase Boundary Line form single-phase homogeneous systems while those mixtures represented by the area to the right of the aforesaid Phase Boundary Line are two-phase heterogeneous systems. However, it has been found that when the concentration of alkali metal hydroxide is greater than about 40 percent and the alkali metal isobutyrate concentration is greater than about 5 percent, the alkali metal salt phase is solid i.e., non-liquid at temperatures below about 100 F. Consequently, it is necessary to have a co-solvent or liquefier present such as an alkali metal salt of alkyl phenols, i.e., cresylates, lower aliphatic alcohols, lower ketones, etc.

The addition of such a co-solvent or liquefier shifts the phase boundary line to the right on the ternary diagram as indicated by Phase Boundary Lines GE and HF. Thus, for example, for the system potassium isobutyrate- 

1. A METHOD OF REGENERATING AQUEOUS ALKALI METAL HYDROXIDE REAGENT CONTAINING MERCAPTIDES WHICH COMPRISES IN A CYCLIC MANNER (1) IN A REACTION ZONE MIXING (A) FOULED AQUEOUS ALKALI METAL HYDROXIDE REAGENT CONTAINING MERCAPTIDES WITH (B) TREATING AGENT SUBSTANTIALLY DEVOID OF CRESYLATES CONSISTING ESSENTIALLY OF ALKALI METAL SALT OF A SOLUTIZER AND LIQUEFIER TO OBTAIN A FOULED MIXTURE HAVING THE FOLLOWING CHARACTERISTICS: (1) THE FOULED MIXTURE FORMS A TWO LIQUID PHASES SYSTEM AT A TEMPERATURE WITHIN THE TEMPERATURE RANGE OF ABOUT 60*F. TO ABOUT 150*F. CONSISTING OF AN UPPER LIQUID AQUEOUS SOLUTIZER SALT PHASE AND A LOWER AQUEOUS ALKALI METAL HYDROXIDE PHASE; (II) THE FOULED MIXTURE CONTAINS ONLY A LIQUEFYING CONCENTRATION OF LIQUEFIER TO MAINTAIN THE AFORESAID UPPER AQUEOUS SOLUTIZER SALT PHASE LIQUID AT A TEMPERATURE WITHIN THE AFORESAID TEMPERATURE RANGE; (III) THE AFORESAID LIQUEFIER IS SELECTEF FROM THE GROUP CONSISTING OF ALIPHATIC ALCOHOLS HAVING NOT MORE THAN FIVE CARBON ATOMS IN THE MOLECULE AND WATER-SOLUBLE KETONES, (2) 